Dyes containing thiophene radicals

ABSTRACT

The compounds of the general formula ##STR1## where X is fluorine, chlorine, bromine, SO 2  E or unsubstituted or substituted hydroxyl or mercapto, E is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, chlorine or unsubstituted or substituted hydroxyl or amino, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, T is hydrogen, C 1  -C 4  -alkyl, a radical which can be introduced by electrophilic substitution or a radical of the formula --CH═B, in which B is a radical of a methylene-active compound or of an amine, and K is a radical of a coupling component, are very useful for dyeing synthetic fibers or plastics.

This application is a continuation of application Ser. No. 07/532,663, filed Jun. 4, 1990, now abandoned, which is a divisional of Ser. No. 07/205,359, filed Jul. 27, 1988, now abandoned, which is a divisional of Ser. No. 06/860,573, filed May 7, 1986, now abandoned.

SUMMARY OF THE INVENTION

The present invention relates to compounds of the general formula I ##STR2## where X is fluorine, chlorine, bromine, SO₂ E or unsubstituted or substituted hydroxyl or mercapto, E is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, chlorine or unsubstituted or substituted hydroxyl or amino, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, T is hydrogen, C₁ -C₄ -alkyl, a radical which can be introduced by electrophilic substitution or a radical of the formula --CH═B, in which B is a radical of a methylene-active compound or of an amine, and K is a radical of a coupling component.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples of radicals X, in addition to those stated above, are alkoxy, cycloalkoxy, aralkoxy and aryloxy, as well as the corresponding mercapto radicals. Specific examples are OH, OCH₃, OC₂ H₅, OC₃ H₇, OC₄ H₉, OCH₂ C₆ H₅, OC₆ H₁₁, OC₆ H₅, OC₆ H₄ CH₃, OC₆ H₄ Cl, SH, SC₂ H₅, SC₃ H₇, SC₄ H₉, SCH₂ C₆ H₅, SC₂ H₄ OH, SCH₂ COOCH₃, SCH₂ COOC₂ H₅, SC₆ H₁₁, SC₆ H₅ and SC₆ H₄ CH₃.

E is, for example, CH₃, C₂ H₅, C₃ H₇, C₄ H₃, C₆ H₁₃, C₆ H₁₁, C₈ H₁₇, C₆ H₅ --CH₂, C₆ H₅ --CH₂ --CH₂, C₆ H₅, Cl--C₆ H₄, C₄ H₉ --C₆ H₄, Cl, OH, CH₃ O, C₂ H₅ O, C₃ H₇ O, C₄ H₅ O, C₆ H₅ --CH₂ O, C₆ H₅ --CH₂ --CH₂ O, C₆ H₅ O, ClC₆ H₄ O, CH₃ C₆ H₄ O, NH₂, NNCH₃, N(CH₃)₂, NHC₂ H₅, N(C₂ H₅)₂, NHC₄ H₉, N(C₄ H₉)₂, NHC₆ H₅, NHC₆ H₅, NHC₆ H₄ --CH₃, NHC₆ H₄ Cl or N(CH₃)C₆ H₄.

Specific examples of radicals Y, in addition to those stated above, are: CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, C₄ H₉ CO, C₅ H₁₁ CO, C₇ H₁₅ CO, ##STR3## C₆ H₅ CO, CH₃ C₆ H₄ CO, ClC₆ H₄ CO, (CH₃)₂ C₆ H₃ CO, H₃ COC₆ H₄ CO, Cl₂ C₆ H₃ CO, CH₃ SO₂. C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO₂, CH₃ C₆ H₄ SO₂, ClC₆ H₄ SO₂, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₅, COOC₆ H₁₃, COOC₈ H₁₇, ##STR4## COOC₂ H₄ OH, COOC₃ H₆ OH, COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ H₉, COOC₆ H₅, COOC₄ H₄ CH₃, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₁₃, CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₃ H₇)₂, CON(C₄ H₉)₂, ##STR5##

Examples of radicals T which can be introduced by electrophilic substitution are Cl, Br, NO, NO₂, SO₃ H, CHO, CN and acyl, where acyl is, for example CH₃ CO, C₂ H₅ CO, C₆ H₅ CO, CH₃ SO₂, C₂ H₅ SO₂ or C₆ H₅ SO₂.

Methylene-active compounds of the formula H₂ B are, for example, compounds of the formula ##STR6## where Z hydrogen is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl benzimidazolyl, benzoxazolyl, benzthiazolyl, substituted benzoxazolyl, substituted benzimidazolyl or substituted benzthiazolyl or is a radical of a compound of the formula ##STR7##

Specific examples of important compounds of the formula ##STR8## are H₂ C(CN)₂, ##STR9##

Examples of amine radicals B are ═N--C₆ H₅, ═N--C₆ H₄ CH₃ or generally radicals of Schiff's bases of the amines.

Alkyl radicals T are, for example, CH₃, C₂ H₅, C₃ H₇ or C₄ H₉.

The diazo components in which T is H or C₁ -C₄ -alkyl can be prepared by reacting a compound of the formula II ##STR10## with a sulfur donor. Radicals T may be introduced into the diazo components in which T is H by electrophilic substitution by a conventional method.

Furthermore, the diazo component in which T is H and X is OH may be prepared by reacting the compound of the formula

    ClCH.sub.2 COCl

with malodinitrile and then reacting the produce with a sulfide.

The preparation of the diazo components is described in detail in European Patent Application 86102603.7.

The coupling components of the formula HK are preferably derived from aniline, α-naphthylamine, pyrazole, aminopyrazole, indole, thiazole, thiophene, phenol, naphthol, tetrahydroquinoline, pyridone or pyridine series, those of the aniline, pyrazole, pyridine, thiophene and thiazole series being preferred.

The coupling components HK are in particular of the general formula ##STR11## where B¹ is hydrogen or B², B² is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aryl or acyl, R¹ is hydrogen, alkyl, aralkyl or aryl, R² is hydrogen or R³, R³ is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aralkyl or aryl, R⁴ and R⁵ independently of one another are each hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino or acylamino, R⁶ is cyano, carbamyl, nitro, acetyl or carbalkoxy and R⁷ is unsubstituted or substituted phenyl, alkyl, aralkyl, halogen, substituted hydroxyl or mercapto.

Examples of radicals B², in addition to those stated above, are C₁ -C₆ -alkyl which may be substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenylethoxycarbonyl, and phenyl and cyclohexyl.

Specific examples of radicals B² are:

1) Unsubstituted or substituted alkyl, such as CH₃, C₂ H₅, C₃ H₇, CH(CH₃)₂, C₄ H₉, CH₂ CH(CH₃)₂, ##STR12## C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OC₃ H₇, C₂ H₄ OC₄ H₉, C₂ H₄ OC₆ H₅, C₂ H₄ OC₆ H₁₁, C₂ H₄ CN, C₅ H₁₀ CN, C₆ H₁₂ CN, C₂ H₄ OC₂ H₄ CN, C₃ H₆ OC₂ H₄ CN, C₃ H₆ OCH₃, C₃ H₆ OC₂ H₅, C₃ H₆ OC₃ H₇, C₃ H₆ OC₄ H₉, ##STR13## C₃ H₆ OC₆ H₁₁, C₃ H₆ OC₈ H₁₇, C₃ H₆ OCH₂ C₆ H₅, C₃ H₆ OC₂ H₄ C₆ H₅, C₃ H₆ OC₂ H₄ OC₆ H₅, C₃ H₆ OC₆ H₅, C₃ H₆ OC₂ H₄ OH, C₃ H₆ OC₄ H₈ OH, C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OCH(CH₃)₂, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₂ H₄ OCH₂ C₆ H₅, C₃ H₆ OC₆ H₅, C₃ H₆ OC₄ H₈ OCH₃, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉. ##STR14## and the corresponding radicals in which two C₂ H₄ O, C₃ H₆ O, ##STR15## groups are present, and ##STR16##

2. Unsubstituted or substituted cycloalkyl: ##STR17##

3. Unsubstituted or substituted aralkyl: CH₂ --C₆ H₅, C₂ H₄ --C₆ H₅, ##STR18## and those radicals containing C₆ H₄ CH₃ and C₆ H₄ OCH₃ instead of C₆ H₅.

4. Unsubstituted or substituted phenyl: C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₃ (OCH₃)₂, C₆ H₄ Cl and C₆ H₂ (OCH₃)₂ Cl.

5. The radicals CH₂ CH═CH₂, CH₂ COOCH₃, (CH₂)₅ COOCH₃, (CH₂)₅ COOC₂ H₅, ##STR19## were n is 2, 3, 4 or 6.

6. Acyloxy radicals: (CH₂)₂ OCHO, (CH₂)₂ OCO(CH₂)_(n) CH₃, (C₂ H₄ O)₂ CHO, (C₂ H₄ O)₂ CO(CH₂)_(n) CH₃, (CH₂)₃ O(CH₂)₂ OCHO, (CH₂)₃ O(CH₂)₂ OCO(CH₂)_(n) CH₃, (CH₂)₂ O(CH₂)₂ OCHO and (CH₂)₂ O(CH₂)₄ OCO(CH₂)_(n) CH₃, where n is 0 to 7, ##STR20## (CH₂)₂ OCOC₆ H₅, (CH₂)₂ OCOC₆ H₄ CH₃, (CH₂)₂ OCOC₆ H₄ Cl, (CH₂)₂ OCONHCH₃, (CH₂)₂ OCONHC₄ H₉, ##STR21## (CH₂)₂ OCONHC₆ H₅, and the corresponding radicals containing (CH₂)₃ or (CH₂)₄ instead of (CH₂)₂.

7. Acyl radicals: CHO and CH₃ (CH₂)_(n) CO, where n is from 0 to 7, C₆ H₅ CO, CH₃ C₆ H₄ CO, C₆ H₅ CH₂ CO, C₆ H₅ OCH₂ CO, CH₃ SO₂, C₂ H₅ SO₂, C₆ H₅ SO₂ and CH₃ C₆ H₄ SO₂.

Specific examples of radicals R¹, in addition to those stated above, are methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- and p-tolyl and o-, m-and p-chlorophenyl.

Examples of radicals R³, in addition to those mentioned above, are C₁ -C₆ -alkyl which may be substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxylakanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenylethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenylethoxycarbonyl, and phenyl, benzyl, phenethyl and cyclohexyl,

Specific examples of radicals R³ are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonylyoxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethy, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl.

Examples of suitable radicals R⁴ and R⁵ are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy and C₁ -C₄ -alkoxycarbonylamino, and benzoylamino or C₁ -C₆ -alkanoylamino which is unsubstituted or substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy, and C₁ -C₄ -alkylsulfonylamino or -dialkylaminosulfonylamino.

Examples of radicals R⁶ in addition to those mentioned above are aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- and sec.-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- and isopropoxyethoxycarbonyl and n-, iso- and sec.-butoxyethoxycarbonyl.

Examples of radicals R⁷ are C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, phenoxy, benzyloxy, phenyl, chlorine, bromine, nitro, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -mono- and dialkylamino, C₁ -C₄ -alkoxyethoxy, C₁ -C₄ -alkyl- or phenylmercapto, C₁ -C₅ -alkanoylamino, such as acetylamino, propionylamino, butyrylamino or valerylamino, monosubstituted or polysubstituted phenyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl and benzyl.

The compounds of the formula I have yellow to greenish blue hues and are particularly useful for dyeing polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers. As a rule, the dyeings obtained have good or very good fastness properties, particularly on polyesters.

Dyes having a suitable constitution are dischargeable under reduced conditions and/or under alkaline and reducing conditions.

Suitable discharging agents are the conventionally used ones, for example tin(II) chloride, sodium bisulfite, sodium dithionite or hydroxymethanesulfonic acid. The discharge process too can be carried out in a conventional manner.

Some of the compounds of the formula I are very useful for dyeing thermoplastics, such as polystyrene, polymethacrylates, polycarbonates, nylon and styrene/acrylic acid/butadiene copolymers, since they possess high color strength and good lightfastness and heat resistance. Further more, many novel dyes can be used for dyeing and/or printing polyester/cotton blends by the process described in German Patent 1,811,796, the resulting dyeings having good lightfastness and fastness to washing.

The compounds of the formula I can be prepared by a conventional method. Details are given in the Examples, in which parts and percentages are by weight, unless stated otherwise.

Of particular importance are compounds of the formulae I a ##STR22## and I b ##STR23## where X¹ is chlorine, bromine, hydroxyl, C₁ -C₄ -alkoxy or -alkylthio, methylsulfonyl, phenylsulfonyl, phenoxy or phenylthio, Y¹ and Z¹ are each cyano, a carboxylic ester group or substituted carbamyl, T¹ is formyl, nitro or cyano and K¹ is a radical of a coupling component of the aniline, thiazole, pyrazole, thiophene or pyridine series.

Compounds of the formulae Ia and Ib in which X¹ is chlorine, ethoxy or phenylmercapto, Y¹ is cyano, T¹ is formyl, Z¹ is cyano, a carboxylic ester group or substituted carbamyl and K is a radical of a coupling component of the aniline, thiazole, thiophene or pyridine series, are particularly useful industrially.

Other particularly important dyes are those of the general formula IIa ##STR24## where X¹, Y¹ and T¹ have the stated meanings, B³ is hydrogen or B⁴, and B⁴ is C₂ -C₈ -alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxy, benzyloxy or phenoxy, or is phenyl which is unsubstituted or substituted by methyl or methoxy. Preferred carboxylic ester groups Y¹ are COOCH₃ and COOC₂ H₅.

Examples of particularly preferred radicals B³ and B⁴ are hydrogen and C₂ H₅, C₃ H₇, C₄ H₉, ##STR25## C₆ H₁₁, C₆ H₅, C₆ H₄ CH₃, C₆ H₄ OCH₃, C₂ H₄ OH, C₃ H₆ OH, C₂ H₄ OCH₃, C₃ H₆ OCH₃, C₂ _(H) ₄ OC₂ H₅, C₂ H₄ OC₄ H₉, C₃ H₆ OC₂ H₅, C₂ H₄ OC₂ H₄ OH, C₃ H₆ OC₂ H₄ OH, C₃ H₆ OC₄ H₈ OH, C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₂ H₄ OC₂ H₄ OCO(CH₂)_(m) CH₃, C₃ H₆ OC₂ H₄ OCO(CH₂)_(m) H₃, C₃ H.sub. 6 OC₄ H₈ OC₄ H₉, C₂ H₄ OC₂ H₄ OCO(CH₂)_(m) CH₃, C₃ H₆ OC₂ H₄ OCO(CH₂)_(m) CH₃, C₃ H₆ OC₄ H₈ OCO(CH₂)_(m) CH₃, C₂ H₄ OCO(CH₂)_(m) CH₃, C₃ H₆ OCO(CH₂)_(m) CH₃, C₃ H₆ OCH₂ C₆ N₅ and C₃ H₆ OC₂ H₄ OC₆ H₅, where m is from 1 to 4.

Examples of particularly preferred combinations of B³ and B⁴ are hydrogen and C₂ H₄ OC₂ H₄ OCOCH₃, C₂ H₄ OC₂ H₄ OCOC₂ H₅, C₃ H₆ OH, C₃ H₆ OC₄ H₈ OCOCH₃, C₃ H₆ OC₄ H₈ OCOC₂ H₅, C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₃ H₆ OCH₂ C₆ H₅, C₃ H₆ OC₂ H₄ OC₆ H₅ or C₃ H₆ OCH₂ CH(C₂ H₅)C₄ H₉, and C₂ H₅, C₂ H₄ OCH₃, C₃ H₆ OCH₃, CH(CH₃)₂ or C.sub. 4 H₉ in combination with C₂ H₄ OC₂ H₄ OCOCH₃, C₃ H₆ OC₄ H₈ OH, C₃ H₆ OC₄ H₈ OCHO, C₃ H₆ OC₄ H₈ OCOCH₃, C₃ H₆ OC₄ H₈ OCOC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉ or C₃ H₆ OC₂ H₄ OC₆ H₅ and furthermore C₂ H₄ OH, C₃ H₆ OH, C₂ H₄ OCOCH₃, C₂ H₄ OCOC₂ H₅, C₃ H₆ OCOCH₃ or C₃ H₆ OCOC₂ H₅ in combination with C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₆ H₄ OCH₃ or C₆ H₅.

The process for the preparation of acyloxyalkyl-substituted or acyloxyalkoxyalkyl-substituted 2,6-diaminopyridines which are free of by-products is also particularly important.

Previously, azo dyes containing such coupling components had to be prepared by subsequent acylation of the corresponding hydroxyl-containing dyes in anhydrous organic solvents with acyl halides or anhydrides since the coupling components themselves preferentially undergo N-acylation under these conditions, and the N-acyl-2,6-diaminopyridines are not capable of coupling.

According to the invention, the coupling components are prepared by adding not less than an equivalent amount of sulfuric acid to a solution or suspension of the hydroxyl-containing substituted pyridine in the desired organic acid and stirring the mixture at from 20° to 100° C., preferably from 20° to 50° C. The degree of acylation is dependent on the water content and reaches 100% in an anhydrous medium. However, the absence of water and 100% conversion are not essential in every case in order to achieve optimum dyeing properties. An adequate conversion in most cases is 70-90%, which does not require the absence of water and advantageously allows the acylation to be combined with the preparation of the hydroxyalkylaminopyridine.

EXAMPLE 1

4.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene in 30 parts by volume of 85% strength sulfuric acid were stirred at no higher than 30° C., 8.3 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C., and the mixture was then stirred for a further 4 hours at this temperature.

The resulting diazonium salt solution was slowly run, at 0° C., into a solution of 5.8 parts of N,N-diallyl-5-aminoacetanilide in a mixture of 25 parts by volume of dimethylformamide, 125 parts of water, 300 parts of ice, 20 parts by volume of 32% strength hydrochloric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 9 parts of the dye of the formula ##STR26## which dyes polyester fibers in fast blue hues.

EXAMPLE 2

4.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were diazotized by a method similar to that described in Example 1. The diazonium salt solution was added dropwise at 0° C., to a solution of 8.8 parts of o-(bis-acetoxyethyl)-amino-p-acetanisidine in a mixture of 125 parts of water, 350 parts of ice, 1 part of 96% strength sulfuric acid and 0.5 pat of amidosulfonic acid. When coupling was complete, the dye was filtered under suction, washed until neutral and dried to give 9.5 parts of a greenish black powder of the formula ##STR27## which dyes polyester fabric in fast greenish blue hues.

The dyes characterized in the Table below are obtained similarly to Examples 1 and 2.

    __________________________________________________________________________      ##STR28##                                                                     Example                                  Dyeing on                             No.  T    X   Y      K                   polyester                             __________________________________________________________________________     3    CHO  Cl  CN                                                                                     ##STR29##          blue                                  4    CHO  Cl  CN                                                                                     ##STR30##          bluish violet                         5    CHO  Cl  CN                                                                                     ##STR31##          blue                                  6    CHO  Cl  CN                                                                                     ##STR32##          blue                                  7    CHO  Cl  CN                                                                                     ##STR33##          blue                                  8    CHO  Cl  CN                                                                                     ##STR34##          blue                                  9    CHO  Cl  CN                                                                                     ##STR35##          blue                                  10   CHO  Cl  CN                                                                                     ##STR36##          blue                                  11   CHO  Cl  CN                                                                                     ##STR37##          reddish blue                          12   CHO  Cl  CN                                                                                     ##STR38##          reddish blue                          13   CHO  Cl  CN                                                                                     ##STR39##          bluish violet                         14   CHO  Cl  CN                                                                                     ##STR40##          violet                                15   CHO  Cl  CN                                                                                     ##STR41##          greenish blue                         16   CHO  Cl  CN                                                                                     ##STR42##          greenish blue                         17   CHO  Cl  CN                                                                                     ##STR43##          greenish blue                         18   CHO  Cl  CN                                                                                     ##STR44##          greenish blue                         19   CHO  Cl  CN                                                                                     ##STR45##          greenish blue                         20   CHO  Cl  CN                                                                                     ##STR46##          greenish blue                         21   CHO  Cl  CN                                                                                     ##STR47##          greenish blue                         22   CHO  Cl  CN                                                                                     ##STR48##          blue                                  23   CHO  Cl  CN                                                                                     ##STR49##          blue                                  24   CHO  Cl  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR50##          blue                                  25   CHO  Cl  CN                                                                                     ##STR51##          blue                                  26   CHO  Cl  CN                                                                                     ##STR52##          blue                                  27   CHO  Cl  CN                                                                                     ##STR53##          blue                                  28   CHO  Cl  CN                                                                                     ##STR54##          blue                                  29   CHO  Cl  CN                                                                                     ##STR55##          blue                                  30   CHO  Cl  CN                                                                                     ##STR56##          blue                                  31   CHO  Cl  COOCH.sub.3                                                                            ##STR57##          blue                                  32   CHO  Cl  SO.sub.2 CH.sub.3                                                                      ##STR58##          blue                                  33   CHO  Cl  CONH.sub.2                                                                             ##STR59##          reddish blue                          34   CHO  Cl  CON(CH.sub.3).sub.2                                                                    ##STR60##          blue                                  35   CHO  Cl  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR61##          blue                                  36   CHO  Cl  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR62##          bluish violet                         37   CHO  Cl  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR63##          blue                                  38   CHO  Cl  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR64##          greenish blue                         39   CHO  Br  CN                                                                                     ##STR65##          violet                                40   CHO  Br  CN                                                                                     ##STR66##          bluish violet                         41   CHO  Br  CN                                                                                     ##STR67##          blue                                  42   CHO  Br  CN                                                                                     ##STR68##          greenish blue                         43   CHO  Br  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR69##          blue                                  44   CHO  F   CN                                                                                     ##STR70##          blue                                  45   CHO  F   CN                                                                                     ##STR71##          reddish blue                          46   CHO  F   CN                                                                                     ##STR72##          blue                                  47   CHO  F   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR73##          reddish blue                          48   CHO  Cl  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR74##          blue                                  49   CHO  Cl  CONH.sub.2                                                                             ##STR75##          blue                                  50   CHO  Cl  NO.sub.2                                                                               ##STR76##          blue                                  51   CHO  Cl  CON(CH.sub.3).sub.2                                                                    ##STR77##          blue                                  52   CHO  Cl  SO.sub.2 CH.sub.3                                                                      ##STR78##          blue                                  53   CHO  Br  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR79##          blue                                  54   CHO  Cl  CN                                                                                     ##STR80##          blue                                  55   CHO  Cl  CN                                                                                     ##STR81##          blue                                  56   CHO  Br  CN                                                                                     ##STR82##          blue                                  57   CHO  Cl  CN                                                                                     ##STR83##          violet                                58   CHO  Cl  CN                                                                                     ##STR84##          blue                                  59   CHO  Cl  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR85##          blue                                  60   CHO  Cl  CN                                                                                     ##STR86##          yellowish brown                       61   CHO  Cl  CN                                                                                     ##STR87##          red                                   62   CHO  Cl  CN                                                                                     ##STR88##          red                                   63   CHO  Cl  CN                                                                                     ##STR89##          blue                                  64   CHO  Cl  CN                                                                                     ##STR90##          blue                                  65   CHO  Br  CN                                                                                     ##STR91##          blue                                  66   CHO  Cl  CN                                                                                     ##STR92##          blue                                  67   CHO  Cl  CN                                                                                     ##STR93##          violet                                68   CHO  Cl  CN                                                                                     ##STR94##          red                                   69   CHO  Cl  CN                                                                                     ##STR95##          red                                   70   CHO  Cl  CN                                                                                     ##STR96##          blue                                  71   CHO  Cl  CN                                                                                     ##STR97##          blue                                  72   H    Cl  CN                                                                                     ##STR98##          red                                   73   CH.sub.3                                                                            Cl  CN                                                                                     ##STR99##          red                                   74   CH.sub.3                                                                            Cl  CN                                                                                     ##STR100##         red                                   75   CH.sub.3                                                                            Cl  CN                                                                                     ##STR101##         reddish violet                        76   C.sub.2 H.sub.5                                                                     Cl  CN                                                                                     ##STR102##         red                                   77   CH.sub.3                                                                            Br  CN                                                                                     ##STR103##         red                                   78   CN   Cl  CN                                                                                     ##STR104##         blue                                  79   CN   Cl  CN                                                                                     ##STR105##         blue                                  80   CN   Cl  CN                                                                                     ##STR106##         greenish blue                         81   CN   Br  CN                                                                                     ##STR107##         reddish blue                          82   CN   Cl  CN                                                                                     ##STR108##         blue                                  83   NO.sub.2                                                                            Cl  CN                                                                                     ##STR109##         reddish blue                          84   NO.sub.2                                                                            Cl  CN                                                                                     ##STR110##         blue                                  85   NO.sub.2                                                                            Cl  CN                                                                                     ##STR111##         greenish blue                         86   NO.sub.2                                                                            Cl  CN                                                                                     ##STR112##         greenish blue                         87                                                                                   ##STR113##                                                                         Cl  CN                                                                                     ##STR114##         blue                                  88   NO.sub.2                                                                            Br  CN                                                                                     ##STR115##         blue                                  89   NO.sub.2                                                                            Cl  CN                                                                                     ##STR116##         greenish blue                         90   NO.sub.2                                                                            Cl  CN                                                                                     ##STR117##         greenish blue                         91   Br   Cl  CN                                                                                     ##STR118##         bluish red                            92   Br   Cl  CN                                                                                     ##STR119##         bluish violet                         93   Br   Cl  CN                                                                                     ##STR120##         red                                   94   Br   Cl  CN                                                                                     ##STR121##         red                                   95   Br   Cl  CN                                                                                     ##STR122##         bluish violet                         96   Cl   Cl  CN                                                                                     ##STR123##         bluish red                            97   Cl   Cl  CN                                                                                     ##STR124##         reddish blue                          98   Br   Br  CN                                                                                     ##STR125##         reddish blue                          __________________________________________________________________________

EXAMPLE 99

11.7 parts of 2-amino-3-cyano-4-ethoxy-5-formylthiophene in 200 parts by volume of a 3:1 glacial acetic acid/propionic acid mixture and 25 parts by volume of 96% strength sulfuric acid were stirred at no higher than 20° C. 23 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C., and the mixture was then stirred for 1 hour.

The resulting diazonium salt solution was added dropwise, at 0° C., to a solution of 21 parts of o-(bis-acetoxyethyl)-amino-p-acetanisidine in a mixture of 100 parts by volume of dimethylformamide, 500 parts of water, 25 parts by volume of 18% strength hydrochloric acid, 250 parts of ice and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 25 parts of the dye of the formula ##STR126## which dyes polyester fibers in the fast greenish blue hues.

The dyes shown in the Table below were obtained similarly to Example 99.

    __________________________________________________________________________      ##STR127##                                                                    Example                                  Dyeing on                             No.  T    X   Y      K                   polyester                             __________________________________________________________________________     100  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR128##         blue                                  101  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR129##         bluish violet                         102  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR130##         blue                                  103  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR131##         blue                                  104  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR132##         blue                                  105  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR133##         blue                                  106  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR134##         reddish blue                          107  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR135##         reddish blue                          108  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR136##         bluish violet                         109  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR137##         violet                                110  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR138##         greenish blue                         111  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR139##         greenish blue                         112  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR140##         greenish blue                         113  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR141##         greenish blue                         114  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR142##         blue                                  115  CHO  OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR143##         blue                                  116  CHO  OC.sub.2 H.sub.5                                                                   COOCH.sub.3                                                                            ##STR144##         blue                                  117  CHO  OC.sub.2 H.sub.5                                                                   SO.sub.2 CH.sub.3                                                                      ##STR145##         blue                                  118  CHO  OC.sub.2 H.sub.5                                                                   CONH.sub.2                                                                             ##STR146##         reddish blue                          119  CHO  OC.sub.2 H.sub.5                                                                   CON(CH.sub.3).sub.2                                                                    ##STR147##         blue                                  120  CHO  OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR148##         blue                                  121  CHO  OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR149##         bluish violet                         122  CHO  OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR150##         blue                                  123  CHO  OC.sub.2 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR151##         greenish blue                         124  CHO  OCH.sub.3                                                                          CN                                                                                     ##STR152##         violet                                125  CHO  OCH.sub.3                                                                          CN                                                                                     ##STR153##         bluish violet                         126  CHO  OCH.sub.3                                                                          CN                                                                                     ##STR154##         blue                                  127  CHO  OCH.sub.3                                                                          CN                                                                                     ##STR155##         greenish blue                         128  CHO  OCH.sub.3                                                                          CO.sub.2 C.sub.2 H.sub.5                                                               ##STR156##         blue                                  129  CHO  OC.sub.6 H.sub.5                                                                   CN                                                                                     ##STR157##         blue                                  130  CHO  OC.sub.6 H.sub.5                                                                   CN                                                                                     ##STR158##         bluish violet                         131  CHO  SC.sub.6 H.sub.5                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR159##         blue                                  132  CHO  SC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR160##         bluish violet                         133  CHO  SC.sub.6 H.sub.5                                                                   CN                                                                                     ##STR161##         blue                                  134  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR162##         blue                                  135  CHO  OC.sub.2 H.sub. 5                                                                  CN                                                                                     ##STR163##         blue                                  136  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR164##         blue                                  137  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR165##         reddish blue                          138  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR166##         blue                                  139  CHO  OCH.sub.3                                                                          CO.sub.2 C.sub.2 H.sub.5                                                               ##STR167##         blue                                  140  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR168##         yellowish brown                       141  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR169##         red                                   142  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR170##         red                                   143  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR171##         blue                                  144  CHO  OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR172##         blue                                  145  CHO  OCH.sub.3                                                                          CN                                                                                     ##STR173##         blue                                  146  CHO  OC.sub.6 H.sub.5                                                                   CN                                                                                     ##STR174##         blue                                  147  CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR175##         red                                   148  CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR176##         red                                   149  CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR177##         reddish violet                        150  C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR178##         red                                   151  CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR179##         red                                   152  CN   OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR180##         blue                                  153  CN   OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR181##         blue                                  154  NO.sub.2                                                                            OC.sub.2 H.sub.5                                                                   CN                                                                                     ##STR182##         blue                                  __________________________________________________________________________

EXAMPLE 155

5.8 parts of the dye described in Example 12 were dissolved in 60 parts by volume of dioxane, 3.4 parts of ethyl cyanoacetate, 1 part of glacial acetic acid and 1 part of piperidine were added, and the mixture was stirred for 16 hours at room temperature, after which 50 parts of water and 50 parts of ice were added. Stirring was continued for 15 minutes, and the product was filtered off under suction, washed neutral and dried at 50° C. under reduced pressure to give 6.6 parts of the dye of the formula ##STR183## which dyes polyester fibers in medium blue hues.

EXAMPLE 156

5.1 parts of the dye described in example 13 were dissolved in 65 parts by volume of dioxane, 4.2 parts of butyl cyanoacetate, 1 part of glacial acetic acid and 1 part of piperidine were added and the mixture was stirred for 16 hours at room temperature. Thereafter, 50 parts of water and 50 parts of ice were added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral and dried to give 5.9 parts of the dye of the formula ##STR184## which dyes polyester in fast blue hues.

The dyes listed in the Table below were obtained similarly to Examples 155 and 156.

    __________________________________________________________________________      ##STR185##                                                                    Example                                                Dyeing on               No.  X    Y     Y.sup.1                                                                               Y.sup.2    K                    polyester               __________________________________________________________________________     157  Cl   CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR186##          blue                    158  Cl   CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR187##          reddish blue            159  Cl   CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR188##          blue                    160  Cl   CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR189##          blue                    161  Cl   CN    CN     CN                                                                                         ##STR190##          blue                    162  Cl   CN    COCH.sub.3                                                                            COOC.sub.2 H.sub.5                                                                         ##STR191##          blue                    163  Cl   COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                         ##STR192##          blue                    164  Cl   COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                         ##STR193##          blue                    165  Cl   COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                         ##STR194##          blue                    166  Cl   COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR195##          dark blue               167  Cl   COOC.sub.2 H.sub.5                                                                   COCH.sub.3                                                                            COOC.sub.2 H.sub.5                                                                         ##STR196##          dark blue               168  Cl   COOC.sub.2 H.sub.5                                                                   COCH.sub.3                                                                            COCH.sub.3                                                                                 ##STR197##          blue                    169  Cl   COOC.sub.2 H.sub.5                                                                   COCH.sub.3                                                                            CN                                                                                         ##STR198##          dark blue               170  Cl                                                                                   ##STR199##                                                                          CN     COOC.sub.2 H.sub.5                                                                         ##STR200##          dark blue               171  Cl                                                                                   ##STR201##                                                                          CN     COOC.sub.2 H.sub.5                                                                         ##STR202##          blue                    172  Cl   SO.sub.2 CH.sub.3                                                                    CN     COOC.sub.2 H.sub.5                                                                         ##STR203##          dark blue               173  Cl   SO.sub.2 CH.sub.3                                                                    CN     COOC.sub.2 H.sub.5                                                                         ##STR204##          blue                    174  Cl   SO.sub.2 CH.sub.3                                                                    CN     COOC.sub.2 H.sub.5                                                                         ##STR205##          blue                    175  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR206##          reddish blue            176  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR207##          dark blue               177  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR208##          dark blue               178  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR209##          dark blue               179  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR210##          dark blue               180  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR211##          dark blue               181  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR212##          blue                    182  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR213##          blue                    183  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR214##          blue                    184  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR215##          blue                    185  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR216##          violet                  186  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR217##          violet                  187  Cl   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR218##          violet                  188  Cl   CN    CN     CONHCH.sub.3                                                                               ##STR219##          dark blue               189  Cl   CN    CN     CONHC.sub.2 H.sub.5                                                                        ##STR220##          dark blue               190  Cl   CN    CN     SO.sub.2 CH.sub.3                                                                          ##STR221##          dark blue               191  Cl   CN    CN     COCH.sub.3                                                                                 ##STR222##          dark blue               192  Cl   CN    CN     COOCH.sub.3                                                                                ##STR223##          dark blue               193  Cl   CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR224##          blue                    194  Cl   CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR225##          blue                    195  Cl   CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR226##          blue                    196  Cl   CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR227##          dark blue               197  Cl   CN    CN                                                                                     ##STR228##                                                                                ##STR229##          dark blue               198  Cl   CN    CN                                                                                     ##STR230##                                                                                ##STR231##          dark blue               199  Cl   CN    CN                                                                                     ##STR232##                                                                                ##STR233##          dark blue               200  Cl   CN    CN     CONH.sub.2                                                                                 ##STR234##          dark blue               201  Cl   CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR235##          navy blue               202  Cl   CN    COCH.sub.3                                                                            COOC.sub.2 H.sub.5                                                                         ##STR236##          dark blue               203  Cl   CN    CN     CONHCH.sub.3                                                                               ##STR237##          dark blue               204  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR238##          reddish blue            205  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR239##          reddish blue            206  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR240##          blue                    207  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR241##          dark blue               208  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR242##          dark blue               209  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR243##          dark blue               210  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR244##          dark blue               211  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR245##          dark blue               212  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR246##          dark blue               213  Br   CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR247##          dark blue               214  Br   COOC.sub.2 H.sub.5                                                                   CN     CN                                                                                         ##STR248##          blue                    215  Br   COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.9                                                                         ##STR249##          dark blue               216  Br   COOC.sub.2 H.sub.5                                                                   CN     CON(CH.sub.3).sub.2                                                                        ##STR250##          bluish violet           217  Br   CONH.sub.2                                                                           CN     COOC.sub.2 H.sub.5                                                                         ##STR251##          dark blue               218  Br   SO.sub.2 CH.sub.3                                                                    CN     COOC.sub.2 H.sub.5                                                                         ##STR252##          dark blue               219  Br   CON(CH.sub.3).sub.2                                                                  CN     COOC.sub.2 H.sub.5                                                                         ##STR253##          dark blue               220  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR254##          dark blue               221  Br   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR255##          blue                    222  Br   CN    CN     COOCH.sub.3                                                                                ##STR256##          blue                    223  Br   CN    CN     COOCH.sub.3                                                                                ##STR257##          navy blue               224  Cl   CN    CN                                                                                     ##STR258##                                                                                ##STR259##          dark blue               225  F    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR260##          dark blue               226  F    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR261##          dark blue               227  F    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR262##          dark blue               228  F    COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                         ##STR263##          dark blue               229  OC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR264##          dark blue               230  OC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR265##          blue                    231  OC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR266##          dark blue               232  OC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR267##          blue                    233  OC.sub.2 H.sub.5                                                                    CN    CN     CN                                                                                         ##STR268##          dark blue               234  OC.sub.2 H.sub.5                                                                    CN    COCH.sub.3                                                                            COOC.sub.2 H.sub.5                                                                         ##STR269##          dark blue               235  OC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                         ##STR270##          blue                    236  OC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                         ##STR271##          dark blue               237  OC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                         ##STR272##          blue                    238  OC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    COOC.sub. 2 H.sub.5                                                                        ##STR273##          dark blue               239  OC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   COCH.sub.3                                                                            COOC.sub.2 H.sub.5                                                                         ##STR274##          dark blue               240  OC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   COCH.sub.3                                                                            COCH.sub.3                                                                                 ##STR275##          bluish violet           241  OC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   COCH.sub.3                                                                            CN                                                                                         ##STR276##          dark blue               242  OC.sub.2 H.sub.5                                                                     ##STR277##                                                                          CN     COOC.sub.2 H.sub.5                                                                         ##STR278##          dark blue               243  OC.sub.2 H.sub.5                                                                     ##STR279##                                                                          CN     COOC.sub.2 H.sub.5                                                                         ##STR280##          blue                    244  OC.sub.2 H.sub.5                                                                    SO.sub.2 CH.sub.3                                                                    CN     COOC.sub.2 H.sub.5                                                                         ##STR281##          dark blue               245  OC.sub.2 H.sub.5                                                                    SO.sub.2 CH.sub.3                                                                    CN     COOC.sub.2 H.sub.5                                                                         ##STR282##          dark blue               246  OC.sub.2 H.sub.5                                                                    SO.sub.2 CH.sub.3                                                                    CN     COOC.sub.2 H.sub.5                                                                         ##STR283##          blue                    247  OC.sub.2 H.sub.5                                                                    CN    CN     CON(CH.sub.3).sub.2                                                                        ##STR284##          reddish blue            248  OC.sub.2 H.sub. 5                                                                   CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR285##          reddish blue            249  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR286##          dark blue               250  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR287##          dark blue               251  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR288##          dark blue               252  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR289##          dark blue               253  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR290##          dark blue               254  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR291##          blue                    255  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR292##          blue                    256  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR293##          blue                    257  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR294##          blue                    258  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR295##          blue                    259  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR296##          blue                    260  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR297##          dark blue               261  OC.sub.2 H.sub.5                                                                    CN    CN                                                                                     ##STR298##                                                                                ##STR299##          dark blue               262  OC.sub.2 H.sub.5                                                                    CN    CN                                                                                     ##STR300##                                                                                ##STR301##          dark blue               263  OC.sub.2 H.sub.5                                                                    CN    CN                                                                                     ##STR302##                                                                                ##STR303##          dark blue               264  OC.sub.2 H.sub.5                                                                    CN    CN     CONH.sub.2                                                                                 ##STR304##          dark blue               265  OC.sub.2 H.sub.5                                                                    CN    COOC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                         ##STR305##          navy blue               266  OC.sub.2 H.sub.5                                                                    CN    COCH.sub.3                                                                            COOC.sub.2 H.sub.5                                                                         ##STR306##          dark blue               267  OC.sub.2 H.sub.5                                                                    CN    CN     CONHCH.sub.3                                                                               ##STR307##          dark blue               268  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR308##          navy blue               269  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR309##          violet                  270  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR310##          violet                  271  OC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR311##          violet                  272  OC.sub.2 H.sub.5                                                                    CN    CN     CONHCH.sub.3                                                                               ##STR312##          dark blue               273  OC.sub.2 H.sub.5                                                                    CN    CN     CONHC.sub.2 H.sub.5                                                                        ##STR313##          dark blue               274  OC.sub.2 H.sub.5                                                                    CN    CN     SO.sub.2 CH.sub.3                                                                          ##STR314##          dark blue               275  OC.sub.2 H.sub.5                                                                    CN    CN     COCH.sub.3                                                                                 ##STR315##          dark blue               276  OC.sub.2 H.sub.5                                                                    CN    CN     COOCH.sub.3                                                                                ##STR316##          dark blue               277  OCH.sub.3                                                                           CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR317##          bluish violet           278  OC.sub.6 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR318##          bluish violet           279  SC.sub.6 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR319##          bluish violet           280  SC.sub.6 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR320##          dark blue               281  OCH.sub.3                                                                           CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR321##          dark blue               282  OCH.sub.3                                                                           CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR322##          blue                    283  OCH.sub.3                                                                           CN    CN     COOC.sub.4 H.sub.9 (n)                                                                     ##STR323##          blue                    284  OC.sub.6 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR324##          dark blue               285  SC.sub.6 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR325##          dark blue               286  SC.sub.6 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR326##          dark blue               287  SC.sub.6 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR327##          dark blue               288  SC.sub.2 H.sub.5                                                                    CN    CN     COOC.sub.2 H.sub.5                                                                         ##STR328##          dark blue               289  SC.sub.2 H.sub.5                                                                    COOC.sub.2 H.sub.5                                                                   CN     COOC.sub.2 H.sub.5                                                                         ##STR329##          dark                    __________________________________________________________________________                                                            blue               

EXAMPLE 290

a) 18.6 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were suspended in 140 parts by volume of ethanol, and 2 parts of glacial acetic acid and 2 parts of piperidine were added. Thereafter, 50 parts by volume of ethyl cyanoacetate were added dropwise at room temperature and the mixture was stirred for 7 hours at 60° C. It was then introduced into 500 parts of an ice/water mixture, and the precipitate was filtered off under suction, washed with water and dried at 60° C. under reduced pressure to give 20 parts of 2-amino-4-chloro-3-cyano-5-(β-cyano-β-carboethoxyvinyl)-thiophene of the formula ##STR330## which was reacted without further purification.

b) 14 parts of this product were suspended in 100 parts by volume of 85% strength phosphoric acid, and 16 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added slowly at 0°-5° C. After 2 hours at this temperature, the diazonium salt solution was run into a solution of 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 125 parts of water, 500 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure to give 20 parts of the dye described in Example 155, of the formula ##STR331## On polyesters, this dye gives dark blue dyeings having generally good fastness properties.

EXAMPLE 291

14.5 parts of 2-amino-3-cyano-4-ethoxy-5-(β-cyano-β-carboethoxyvinyl)-thiophene were suspended in 160 parts by volume of 85% strength phosphoric acid and dialotized with 16 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) at 0°-5° C. After 2 hours at this temperature, the diazonium salt solution was reacted with 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine similarly to Example 290 to give 20 parts of the dye of the formula ##STR332## which, on polyesters, gives blue dyeings possessing good lightfastness and fastness to dry heat pleating and setting.

EXAMPLE 292

14 parts of 2-amino-4-chloro-3-cyano-5-(β-cyano-β-methylaminocarbonyl)-vinyl)-thiophene were suspended in 120 parts by volume of 85% strength phosphoric acid and reacted with 16 parts of nitrosylsulfuric acid at 0°-5° C., and the mixture was stirred for 2 hours at this temperature. The diazonium salt solution was run slowly into a mixture of 6.5 parts of N,N-diethylaniline, 100 parts of water, 300 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the residue was washed neutral and dried to give 16 parts of the dye of the formula ##STR333## which, on polyesters, gives dark blue dyeings possessing generally good fastness properties.

The compounds characterized in the Table below were obtained similarly to Examples 290-292.

    __________________________________________________________________________      ##STR334##                                                                    Example                                  Dyeing on                             No.  X   Y     Y.sup.1                                                                           Y.sup.2                                                                              K                polyester                             __________________________________________________________________________     293  Br  CN    CN COOCH.sub.3                                                                           ##STR335##      dark blue                             294  Br  CN    CN COOCH.sub.3                                                                           ##STR336##      dark blue                             295  Br  CN    CN COOCH.sub.3                                                                           ##STR337##      blue                                  296  Br  CN    CN COOCH.sub.3                                                                           ##STR338##      blue                                  297  Cl  CN    CN COOC.sub.2 H.sub. 5                                                                   ##STR339##      dark blue                             298  Cl  CN    CN COOC.sub.2 H.sub.5                                                                    ##STR340##      dark blue                             299  Cl  CN    CN COOC.sub.2 H.sub.5                                                                    ##STR341##      dark blue                             300  Cl  CN    CN COOC.sub.2 H.sub.5                                                                    ##STR342##      dark blue                             301  Cl  CN    CN CONHCH.sub.3                                                                          ##STR343##      dark blue                             302  Cl  COOCH.sub.3                                                                          CN COOC.sub.2 H.sub.5                                                                    ##STR344##      dark blue                             303  Cl  SO.sub.2 CH.sub.3                                                                    CN COOC.sub.2 H.sub.5                                                                    ##STR345##      dark blue                             304  Cl  CN    CN COOC.sub.2 H.sub.5                                                                    ##STR346##      reddish blue                          305  F   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR347##      dark blue                             306  F   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR348##      dark blue                             307  F   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR349##      blue                                  308  Cl  CN    CN CN                                                                                    ##STR350##      blue                                  309  OC.sub.2 H.sub.5                                                                   CN    CN COOCH.sub.3                                                                           ##STR351##      dark blue                             310  OC.sub.2 H.sub.5                                                                   CN    CN COOCH.sub.3                                                                           ##STR352##      blue                                  311  OCH.sub.3                                                                          CN    CN COOC.sub.2 H.sub.5                                                                    ##STR353##      dark blue                             312  OC.sub.2 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR354##      dark blue                             313  SC.sub.6 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR355##      dark blue                             314  OC.sub.2 H.sub.5                                                                   CN    CN COOCH.sub.3                                                                           ##STR356##      dark blue                             315  SC.sub.6 H.sub.5                                                                   CN    CN COOC.sub.2 H.sub.5                                                                    ##STR357##      dark blue                             __________________________________________________________________________

The following dyes characterized by the substituents can also be prepared similarly to the methods described:

    __________________________________________________________________________     Example                                                                        No.  T            X    Y  K               Color on polyester                   __________________________________________________________________________     316  CHO          Cl   CN                                                                                 ##STR358##     blue                                 317  CHO          Cl   CN                                                                                 ##STR359##     greenish blue                        318  CHO          Cl   CN                                                                                 ##STR360##     blue                                 319  CHO          Cl   CN                                                                                 ##STR361##     blue                                 320  CHO          Cl   CN                                                                                 ##STR362##     blue                                 321  CHO          Cl   CN                                                                                 ##STR363##     blue                                 322  CHO          Br   CN                                                                                 ##STR364##     blue                                 323  CHO          Cl   CN                                                                                 ##STR365##     blue                                 324  CHO          Cl   CN                                                                                 ##STR366##     blue                                 325  CHO          Cl   CN                                                                                 ##STR367##     reddish blue                         326  CHO          Cl   CN                                                                                 ##STR368##     blue                                 327  CHO          Cl   CN                                                                                 ##STR369##     reddish blue                         328  CHO          Cl   CN                                                                                 ##STR370##     blue                                 329  CHO          Cl   CN                                                                                 ##STR371##     blue                                 330  CHO          Cl   CN                                                                                 ##STR372##     blue                                 331  CHO          Cl   CN                                                                                 ##STR373##     blue                                 332  CHO          Cl   CN                                                                                 ##STR374##     blue                                 333  CN           Cl   CN                                                                                 ##STR375##     blue                                 334  CN           Cl   CN                                                                                 ##STR376##     blue                                 335  NO.sub.2     Cl   CN                                                                                 ##STR377##     greenish blue                        336  NO.sub.2     Cl   CN                                                                                 ##STR378##     blue                                 337  NO.sub.2     Cl   CN                                                                                 ##STR379##     blue                                 338  CN           Cl   CN                                                                                 ##STR380##     blue                                 339  CN           Cl   CN                                                                                 ##STR381##     blue                                 340  CN           Cl   CN                                                                                 ##STR382##     blue                                 341  CHO          Cl   CN                                                                                 ##STR383##     blue                                 342  CHO          Cl   CN                                                                                 ##STR384##     blue                                 343  CHO          Cl   CN                                                                                 ##STR385##     reddish blue                         344  CHO          Cl   CN                                                                                 ##STR386##     blue                                 345  CHO          Cl   CN                                                                                 ##STR387##     blue                                 346  CHO          Br   CN                                                                                 ##STR388##     blue                                 347  CHO          Br   CN                                                                                 ##STR389##     blue                                 348  CHO          C.sub.6 H.sub.5 S                                                                   CN                                                                                 ##STR390##     reddish blue                         349  CHO          C.sub.6 H.sub.5 S                                                                   CN                                                                                 ##STR391##     greenish blue                        350  CHO          OC.sub.2 H.sub.5                                                                    CN                                                                                 ##STR392##     reddish blue                         351  CHO          C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                 ##STR393##     blue                                 352  CHO          C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                 ##STR394##     blue                                 353  CN           Cl   CN                                                                                 ##STR395##     reddish blue                         354  CN           Cl   CN                                                                                 ##STR396##     blue                                 355  H.sub.5 C.sub.2 O.sub.2 C(CN)CCH                                                            Cl   CN                                                                                 ##STR397##     blue                                 __________________________________________________________________________

EXAMPLE 356

2 parts of the dye described in Example 3, in 30 parts by volume of dimethylformamide and 50 parts by volume of glacial acetic acid, were stirred and 0.7 part of aniline was added. Stirring was continued for 12 hours at room temperature and 500 parts of water were added and the mixture was filtered under suction to give 2.2 parts of a powder of the formula ##STR398## which dyes polyester fabric in fast blue hues.

EXAMPLE 357

A suspension of 4 parts of the dye described in Example 3 in 50 parts by volume of dimethylformamide and 2 drops of concentrated sulfuric acid were added to 1.1 parts of phenylhydrazine in 40 parts by volume of ethanol. The mixture was stirred for 12 hours at 25° C., after which 500 parts of water were added and the dye of the formula ##STR399## was filtered off under suction and dried. 5 parts of a black powder which dyes polyester fabric in fast blue hues were obtained.

EXAMPLE 358

2.3 parts of the dye described in Example 23 were stirred in 50 parts by volume of formic acid, 0.5 part of hydroxylamine hydrochloride and 0.5 part of sodium formate for 12 hours at room temperature. 400 parts of water were added, after which the mixture was filtered under suction to give 2.4 parts of the dye of the formula ##STR400## which dyes polyester fabric in fast blue hues.

EXAMPLE 359

18.7 parts of 2-amino-3-cyano-4-chloro-5-formylthiophene in 120 parts by volume of glacial acetic acid and 40 parts by volume of propionic acid were stirred for 1 hour at room temperature, after which the mixture was cooled to 0°-5° C., 31 parts of 42% strength nitrosylsulfuric acid were added and stirring was continued for about one hour at this temperature.

The coupling component employed was obtained as follows: a thoroughly stirred mixture of 17 parts (based on dry substance) of water-moist 2-chloro-3-cyano-4-methyl-6-aminopyridine (obtained, for example, by the process described in German Patent 2,260,827), 20 parts by volume of isobutanol, 18 parts of 3-aminopropyl 4-hydroxybutyl ether and 8 parts of sodium carbonate was heated under a decending condenser for 5 hours at 145°-150° C. until a thin layer chromatogram sowed that conversion was complete. The mixture was cooled to about 100° C., after which 35 parts of acetic acid were added dropwise and 15 parts of 96% strength sulfuric acid were introduced dropwise at 35°-40° C. with further slight cooling. Stirring was continued for 3 hours, after which about 92% of the hydroxy compound were found to be acetylated. The solution of the diazonium salt was run into a thoroughly stirred mixture of 100 parts of the resulting coupling component, 300 parts of ice and 100 parts of water, and stirring was continued for about 2 hours at 0°-5° C. until the diazonium salt solution had been consumed. Thereafter, the coupling mixture was filtered under suction and the residue was washed neutral and dried at 80° C. The greenish black powder contains about 90% of the compound of the formula ##STR401## [λ_(max) : 546 nm (9:1 dimethylformamide/acetic acid)] as well as about 10% of the non-acetylated hydroxy compound.

The dye mixture possesses very good tinctorial properties and, on polyester, gives very deep, brilliant, reddish violet dyes possessing very good lightfastness and fastness to plating.

EXAMPLE 360

When an equivalent amount of the coupling component described below was used under the preparation conditions of the above example, the reddish blue dye (λ_(max) : 572 nm, 9:1 dimethylformamide/acetic acid) of the formula ##STR402## was obtained. The product still contained about 5% of the hydroxy compound.

The coupling component used was obtained as follows: 45 parts of 2-chloro-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine (obtained as described in German Patent 2,260,827) were stirred in the presence of one part of p-toluenesulfonic acid in 37 parts of aniline for one hour at 125° C. A total of 10 parts of sodium carbonate were added at 135° C. in three portions at 10 minute intervals, and stirring was continued for about 4 hours at 145° C. until a thin layer chromatogram showed that conversion was complete. Excess aniline was distilled off under reduced pressure, and the hot melt was discharged on to 200 parts by volume of hot water. The aqueous solution was decanted, and the remaining melt was stirred several times with hot water containing acetic acid and was separated off cold. After drying, 14.2 parts of the melt, consisting of 2-phenylamino-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine, were dissolved in 50 parts by volume of glacial acetic acid, and 6 parts of 96% strength sulfuric acid were added dropwise. The mixture was stirred for 3 hours at 60° C., after which the solution was used directly in the coupling reaction described.

The dyes listed in Table I were also obtained in a similar manner, these dyes having a similar property spectrum. The λ_(max) values were determined in a 9:1 mixture of dimethylformamide and acetic acid.

                                      TABLE 1                                      __________________________________________________________________________      ##STR403##                                                                    Exam-                                                                          ple                                λmax                                 No. X       Y  R.sup.1 R.sup.2     [nm]                                        __________________________________________________________________________     361 Cl      CN H       C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub.2                                    H.sub.5     545.5                                       362 Cl      CN H       C.sub.3 H.sub.6 OC.sub.2 H.sub.7 OC.sub.2 H.sub.5                                          547                                         363 Cl      CN H       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9                                          546.8                                       364 Cl      CN C.sub.2 H.sub.4 OCH.sub.3                                                               ##STR404## 565                                         365 Cl      CN                                                                                 ##STR405##                                                                             ##STR406## 567                                         366 Cl      CN                                                                                 ##STR407##                                                                             ##STR408## 573                                         367 OC.sub.2 H.sub.5                                                                       CN H       C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                               538                                         368 OC.sub.2 H.sub.5                                                                       CN H       C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                          540                                         369 OC.sub.2 H.sub.5                                                                       CN C.sub.3 H.sub.6 OCOCH.sub.3                                                             ##STR409## 560.5                                       370 OC.sub.2 H.sub.5                                                                       CN C.sub.3 H.sub.6 OH                                                                      ##STR410## 569                                         371                                                                                 ##STR411##                                                                            CN H       C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                               540                                         372                                                                                 ##STR412##                                                                            CN H       C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                               540                                         __________________________________________________________________________

EXAMPLE 373

14.6 parts of 2-amino-3-cyano-4-ethoxy-5-(2'-cyano-2'-carbethoxyvinyl)-thiophene were diazotized similarly to the procedure described in Example 359 but using half the amount of reagents and assistants, and the product was coupled to 2-(4'-acetoxybutoxy-3'-propylamino-3-cyano-4-methyl-6-aminopyridine. This gives a bluish black powder of the formula ##STR413## which still contains about 10% of the hydroxy compound and dyes polyester materials in medium blue hues which have very good lightfastness, fastness to washing and fastness to plating.

The diazo component was obtained as follows: 60 parts of 2-amino-3-cyano-4-ethoxythiophene-5-carbaldehyde in 200 parts by volume of dimethylformamide and 57 parts of ethyl cyanoacetate were stirred at room temperature. 10 parts by volume of a saturated aqueous sodium acetate solution were added dropwise, and stirring was continued for 2 hours at 40° C. Precipitation was completed by adding 1,000 ml of ice-cold methanol, and the product was filtered off, washed first with ice-cold methanol and then with water, and dried at 60° C. Yield: 60 parts (67.4%).

EXAMPLE 374

The procedure described in Example 359 was used, but with half the amount of reagents and assistants, and 14.1 parts of 2-amino-3-cyano-4-chloro-5-(2'-cyano-2'-carbethoxyvinyl)-thiophene were diazotized and the product coupled to 2-(4'-acetoxybutoxy)-3'-propylamino-3-cyano-4-methyl-6-(3'-acetoxypropylamino) -pyridine.

This gives a black powder which consists of 90% of the compound of the formula ##STR414## (λ_(max) =585.5 nm; acetone) and dyes polyester in medium blue hues which have very good lightfastness, fastness to washing and fastness to plating.

The diazo component was obtained by a method similar to that described in Example 373, and the coupling component was obtained as follows:

45 parts of 2-chloro-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine (obtained as described in German Patent 2,260,827) were stirred for 5 hours at 145° C. in the presence of 14 parts of sodium carbonate in 33 parts of 3-aminopropyl 4-hydroxybutyl ether, and the mixture was cooled to 100° C. and discharged on to 120 parts by volume of glacial acetic acid. 41 g of 96% strength sulfuric acid were then added dropwise at 30° C. The mixture was stirred for 3 hours at 40° C., after which a quarter of the solution was converted to the dye, as described above.

The dyes in Table 2, which have similar properties, were obtained in a similar manner. The λ_(max) values were determined in acetone, except for those marked with *, which were measured in a 9:1 dimethylformamide/acetic acid mixture.

                                      TABLE 2                                      __________________________________________________________________________      ##STR415##                                                                    Example                                 λmax                            No.  T     X   Y  R.sup.1    R.sup.2    [nm]                                   __________________________________________________________________________     375  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN H          C.sub.3 H.sub.6 OCH.sub.3                                                                 583                                    376  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN H                                                                                          ##STR416##                                                                               580.5                                  377  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    594*                                   378  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              597*                                   379  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.2 H.sub.4 OH                                                                        C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    602.3*                                 380  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.3 H.sub.4 OCOCH.sub.3                                                               591.5                                  381  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    591.5                                  382  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              594                                    383  COOC.sub.2 H.sub.5                                                                   OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              594                                    384  CN    OC.sub.2 H.sub.5                                                                   CN H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              583                                    385  CN    OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              595                                    386  CN    OC.sub.2 H.sub.5                                                                   CN C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              595                                    387  CN    Cl  CN C.sub.3 H.sub.6 OCOCH.sub.3                                                                ##STR417##                                                                               613.5*                                 388  CN    Cl  CN C.sub.3 H.sub.4 OH                                                                        C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    605.3*                                 389  CN    Cl  CN H          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    578                                    390  COOCH.sub.3                                                                          Cl  CN H          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              577                                    391  COOC.sub.2 H.sub.5                                                                   Cl  CN H          C.sub.3 H.sub.6 OCH.sub.3                                                                 578                                    392  COOC.sub.2 H.sub.5                                                                   Cl  CN H                                                                                          ##STR418##                                                                               575.5                                  393  COOC.sub.2 H.sub.5                                                                   Cl  CN H                                                                                          ##STR419##                                                                               588                                    394  CN    Cl  CN C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              586                                    395  COOC.sub.2 H.sub.5                                                                   Cl  CN C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4                                      H.sub.9    588                                    396  COOC.sub.2 H.sub.5                                                                   Cl  CN C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              585.5                                  397  COOC.sub.2 H.sub.5                                                                   Cl  CN C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                      H.sub.5    586                                    398  COOC.sub.2 H.sub.5                                                                   Cl  CN C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                               ##STR420##                                                                               612*                                   399  CN    Cl  CN C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3                                              586                                    __________________________________________________________________________

EXAMPLE 400

7.3 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene in 30 parts by volume of 85% strength sulfuric acid were stirred at no higher than 30° C. 8.3 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C., after which stirring was continued for 4 hours at this temperature.

This diazonium salt solution was diluted with 20 ml of concentrated sulfuric acid and then run slowly, at 0° C., into a solution of 6.6 parts of 3-[N,N-di-n-butylamino]-acetanilide in a mixture of 25 parts by volume of dimethylformamide, 125 parts of water, 300 parts of ice and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried, and 12 parts of the dye of the formula ##STR421## were obtained. This dye dyes polyester fibers in fast blue hues.

EXAMPLE 401

7.3 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene were diazotized by a method similar to that described in the Example above.

The diazonium salt solution was added dropwise, at 0° C., to a solution of 5.2 parts of 3-(N,N-diethylamino)-acetanilide in a mixture of 125 parts of water, 350 parts of ice, 10 parts by volume of 32% strength hydrochloric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried, and 10.5 parts of a powder of the formula ##STR422## were obtained. This dye dyes polyester fabric in fast blue hues.

The dyes shown in the Table below were obtained in a similar manner.

    __________________________________________________________________________      ##STR423##                                                                    Example                                          Dyeing on                     No.  T    X           Y      K                   polyester                     __________________________________________________________________________     402  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR424##         greenish blue                 403  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR425##         bluish violet                 404  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR426##         blue                          405  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR427##         blue                          406  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR428##         blue                          407  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR429##         reddish blue                  408  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR430##         bluish violet                 409  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR431##         greenish blue                 410  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR432##         blue                          411  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR433##         blue                          412  CHO  C.sub.6 H.sub. 5 SO.sub.2                                                                  CO.sub.2 C.sub.2 H.sub.5                                                               ##STR434##         blue                          413  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR435##         blue                          414  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR436##         blue                          415  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR437##         blue                          416  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR438##         blue                          417  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR439##         blue                          418  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR440##         blue                          419  CHO                                                                                  ##STR441## CO.sub.2 C.sub.2 H.sub.5                                                               ##STR442##         reddish blue                  420  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR443##         blue                          421  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CONH.sub.2                                                                             ##STR444##         blue                          422  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   NO.sub.2                                                                               ##STR445##         blue                          423  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CON(CH.sub.3).sub.2                                                                    ##STR446##         blue                          424  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   SO.sub.2 CH.sub.3                                                                      ##STR447##         blue                          425  CHO  CH.sub.3 SO.sub.2                                                                          CO.sub.2 C.sub.2 H.sub.5                                                               ##STR448##         blue                          426  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR449##         blue                          427  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR450##         blue                          428  CHO  CH.sub.3 SO.sub.2                                                                          CN                                                                                     ##STR451##         blue                          429  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR452##         violet                        430  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR453##         blue                          431  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CO.sub.2 C.sub.2 H.sub.5                                                               ##STR454##         blue                          432  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR455##         yellowish brown               433  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR456##         red                           434  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR457##         red                           435  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR458##         blue                          436  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR459##         blue                          437  CHO  p-ClC.sub.6 H.sub.4 SO.sub.2                                                               CN                                                                                     ##STR460##         blue                          438  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR461##         blue                          439  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR462##         violet                        440  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR463##         red                           441  CHO  C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR464##         red                           442  CN   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR465##         blue                          443  CN   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR466##         blue                          444  CN   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR467##         greenish blue                 445  CN   CH.sub.3 SO.sub.2                                                                          CN                                                                                     ##STR468##         reddish blue                  446  CN   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR469##         blue                          447  NO.sub.2                                                                            C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR470##         reddish blue                  448  NO.sub.2                                                                            C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR471##         blue                          449  NO.sub.2                                                                            C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR472##         blue                          450  NO.sub.2                                                                            C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR473##         greenish blue                 451                                                                                  ##STR474##                                                                         C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR475##         blue                          452  Cl   C.sub.6 H.sub.5 SO.sub.2                                                                   CN                                                                                     ##STR476##         reddish blue                  453  Br   CH.sub.3 SO.sub.2                                                                          CN                                                                                     ##STR477##         reddish                       __________________________________________________________________________                                                      blue                     

EXAMPLE 454

1.2 parts of sodium phenylsulfinate were added to 2.3 parts of 4-chloro-3-cyano-5-formyl-2-(4'-N,N-dibutylamino-2'-acetylaminophenylazo) -thiophene in 50 parts by volume of dimethylformamide, and the mixture was stirred at room temperature. When the reaction was complete (thin layer chromatogram), the reaction was poured on to 300 parts of water, and the dye formed was isolated. 2.4 parts of the dye of the formula ##STR478## were obtained. This dye dyes polyester fibers in fast blue hues.

The dyes shown in the Table below were obtained by a method similar to Example 454.

    __________________________________________________________________________      ##STR479##                                                                    Example                              Dyeing on                                 No.  T   X    Y    K                 polyester                                 __________________________________________________________________________     455  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR480##       blue                                      456  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR481##       bluish violet                             457  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR482##       blue                                      458  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR483##       blue                                      459  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR484##       blue                                      460  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR485##       blue                                      461  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR486##       reddish blue                              462  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CN                                                                                   ##STR487##       reddish blue                              463  CHO C.sub.6 H.sub.5 SO.sub.2                                                            CO.sub.2 C.sub.2 H.sub.5                                                             ##STR488##       blue                                      __________________________________________________________________________

EXAMPLE 464

2.6 parts of the dye described in Example 413 were dissolved in 80 parts by volume of dioxane, 1.1 parts of ethyl cyanoacetate, 0.4 part of glacial acetic acid and 0.4 part of piperidine were added, and the mixture was stirred for 16 hours at room temperature. 50 parts of water and 50 parts of ice were then added, stirring was continued for 15 minutes, and the product was filtered off under suction, washed neutral and dried at 50° C. under reduced pressure to give 2.8 parts of the dye of the formula ##STR489## which dyes polyester fibers in fast blue hues.

EXAMPLE 465

2.3 parts of the dye described in Example 403 were dissolved in 70 parts by volume of dioxane, 1.4 parts of butyl cyanoacetate, 0.4 part of glacial acetic acid and 0.4 part of piperidine were added and the mixture was stirred for 16 hours at room temperature. 50 parts of water and 50 parts of ice were then added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral and dried to give 2.5 parts of the dye of the formula ##STR490## which dyes polyester fabric in fast blue hues.

The dyes shown in the Table below were obtained similarly to the above Examples.

    __________________________________________________________________________      ##STR491##                                                                    Example                                                 Dyeing on              No.  X        Y     Y.sup.2                                                                             Y.sup.3    K                   polyester              __________________________________________________________________________     466  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   CN                                                                                         ##STR492##         blue                   467  C.sub.6 H.sub.5 SO.sub.2                                                                CN    COCH.sub.3                                                                          COOC.sub.2 H.sub.5                                                                         ##STR493##         blue                   468  C.sub.6 H.sub.5 SO.sub.2                                                                COOC.sub.2 H.sub.5                                                                   CN   COOC.sub.2 H.sub.5                                                                         ##STR494##         blue                   469  C.sub.6 H.sub.5 SO.sub.2                                                                COOC.sub.2 H.sub.5                                                                   CN   COOC.sub. 2 H.sub.5                                                                        ##STR495##         blue                   470  C.sub.6 H.sub.5 SO.sub.2                                                                COOC.sub.2 H.sub.5                                                                   CN   COOC.sub.2 H.sub.5                                                                         ##STR496##         blue                   471  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR497##         reddish blue           472  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR498##         blue                   473  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR499##         blue                   474  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR500##         blue                   475  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR501##         blue                   476  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR502##         violet                 477  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR503##         violet                 478  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR504##         violet                 479  C.sub.6 H.sub. 5 SO.sub.2                                                               CN    CN   CONHCH.sub.3                                                                               ##STR505##         blue                   480  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   CONHC.sub.2 H.sub.5                                                                        ##STR506##         blue                   481  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   SO.sub.2 CH.sub.3                                                                          ##STR507##         blue                   482  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COCH.sub.3                                                                                 ##STR508##         blue                   483  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOCH.sub.3                                                                                ##STR509##         blue                   484  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.4 H.sub.9 (n)                                                                     ##STR510##         greenish blue          485  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.4 H9(n)                                                                           ##STR511##         greenish blue          486  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.4 H.sub.9 (n)                                                                     ##STR512##         blue                   487  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   COOC.sub.4 H.sub.9 (n)                                                                     ##STR513##         blue                   488  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN                                                                                   ##STR514##                                                                                ##STR515##         blue                   489  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN                                                                                   ##STR516##                                                                                ##STR517##         blue                   490  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN                                                                                   ##STR518##                                                                                ##STR519##         blue                   491  C.sub.6 H.sub.5 SO.sub.2                                                                CN    CN   CONH.sub.2                                                                                 ##STR520##         blue                   492  CH.sub.3 SO.sub.2                                                                       CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR521##         blue                   493  CH.sub.3 SO.sub.2                                                                       CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR522##         blue                   494  CH.sub.3 SO.sub.2                                                                       CN    CN   COOC.sub.2 H.sub.5                                                                         ##STR523##         blue                   495  p-ClC.sub.6 H.sub.4 SO.sub.2                                                            CN    CN                                                                                   ##STR524##                                                                                ##STR525##         blue                   __________________________________________________________________________

EXAMPLE 496

14.6 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene were suspended in 50 parts by volume of ethanol, and 1 part of glacial acetic acid and 1 part of piperidine were added. 13 parts by volume of ethyl cyanoacetate were then added dropwise at room temperature, and the mixture was stirred for 5 hours at 60° C. The reaction mixture was poured on to 800 parts of water, and the precipitate was filtered off under suction, washed with water and dried at 50° C. under reduced pressure to give 16 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β-cyano-β-carboethoxyvinyl)-thiophene of the formula ##STR526## which was reacted without further purification.

b) 3.9 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β-cyano-β-carboethoxyvinyl)-thiophene in 35 parts by volume of a 3:1 glacial acetic acid/propionic acid mixture were stirred, and 3.5 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were slowly added at 0°-5° C. After 2 hours at this temperature, the diazonium salt solution was run into a solution of 2 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 25 parts of water, 100 parts of ice, 5 parts by volume of 32% strength hydrochloric acid and 0.2 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure. 4.5 parts of the dye of the formula ##STR527## were obtained. On polyester fibers, this dye gives blue dyeings having in general very good fastness properties.

EXAMPLE 497

3.4 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(β, 62 -dicyanovinyl)-thiophene were suspended in 25 parts by volume of 85% strength phosphoric acid and slowly reacted with 3.5 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) at 0°-5° C., and the mixture was stirred for 2 hours at this temperature. This diazonium salt solution was run slowly into a mixture of 1.5 parts of N,N-diethylaniline, 20 parts of water, 60 parts of ice, 5 parts by volume of 32% strength hydrochloric acid and 0.2 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the dye was washed neutral and dried. 4.2 parts of the dye of the formula ##STR528## were obtained. On polyesters, this dye gives blue dyeings having generally good fastness properties.

The compounds shown in the Table below were obtained in a similar manner.

    __________________________________________________________________________      ##STR529##                                                                    Example                                   Dyeing on                            No.  X    Y     Y.sup.2                                                                           Y.sup.3                                                                              K                polyester                            __________________________________________________________________________     498  CH.sub.3 SO.sub.2                                                                   CN    CN COOCH.sub.3                                                                           ##STR530##      blue                                 499  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOCH.sub.3                                                                           ##STR531##      blue                                 500  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOCH.sub.3                                                                           ##STR532##      greenish blue                        501  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOCH.sub.3                                                                           ##STR533##      greenish blue                        502  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOC.sub.2 H.sub.5                                                                    ##STR534##      blue                                 503  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOC.sub.2 H.sub.5                                                                    ##STR535##      blue                                 504  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOC.sub.2 H.sub.5                                                                    ##STR536##      blue                                 505  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN COOC.sub.2 H.sub.5                                                                    ##STR537##      greenish blue                        506  C.sub.6 H.sub.5 SO.sub.2                                                            CN    CN CONHCH.sub.3                                                                          ##STR538##      blue                                 507  C.sub.6 H.sub.5 SO.sub.2                                                            COOCH.sub.3                                                                          CN COOC.sub.2 H.sub. 5                                                                   ##STR539##      blue                                 __________________________________________________________________________

Examples of suitable dischargeable dyes are the compounds of Examples 21, 22, 113 and 114 and those of Examples 341-355. 

We claim:
 1. A compound of the formula: ##STR540## wherein: X is SO₂ E; --OH; --SH; C₁₋₆ -alkoxy; benzyloxy; phenyloxy; methyl-substituted phenyloxy; chloro-substituted phenyloxy; --S--(C₁₋₆ -alkyl); benzylmercapto; --S--C₂ H₄ OH; --S--CH₂ COOCH₃ ; --S--CH₂ COOC₂ H₅ ; phenylmercapto; or methyl-substituted phenylmercapto;E is C₁₋₈ -alkyl; alkenyl; cycloalkyl; C₇₋₁₀ -aralkyl; aryl; chlorine; hydroxyl; amino; C₁₋₄ -alkoxy; benzyloxy; C₆ H₅ --CH₂ CH₂ --O--; phenyloxy; chlorosubstituted phenyloxy; methyl-substituted phenyloxy; C₁₋₄ alkyl-substituted amino; C₁₋₄ -dialkyl-substituted amino; NHC₆ H₅ ; NHC₆ H₄ CH₃ ; NHC₆ H₄ Cl; or N(CH₃)C₆ H₄ ; Y is cyano; T is hydrogen; C₁ -C₄ -alkyl; Cl; Br; NO; NO₂ ; SO₃ H; CHO; CN; CH₃ CO; C₂ H₅ CO; C₆ H₅ CO; CH₃ SO₂ ; C₂ H₅ SO₂ ; or C₆ H₅ SO₂ ; or --CH═B; R¹ is hydrogen, alkyl, aralkyl or aryl; B is C (CN) (Z) where Z is cyano; nitro; alkanoyl; aroyl; alkylsulfonyl; arylsulfonyl; carboxyl; a carboxylic ester group; unsubstituted carbamyl; substituted carbamyl; or a compound of one of the formulae: ##STR541## and K is a radical derived from a coupling component of the formula: ##STR542## wherein: B¹ is hydrogen or B² ; B² is C₁ -C₆ -alkyl, or C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy, or phenylethoxycarbonyl, or phenyl, or cyclohexyl; R² is hydrogen or R³ ; R³ is C₁ -C₆ -alkyl, C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m-and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenylethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenylethoxycarbonyl, phenyl, benzyl, phenethyl, or cyclohexyl; R⁴ and R⁵, independently of one another, are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, or C₁ -C₄ -alkoxycarbonylamino, benzoylamino, C₁ -C₆ -alkanoylamino, or C₁ -C₆ -alkanoylamino substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy, C₁ -C₄ -alkylsulfonylamino, or -dialkylaminosulfonylamino; R⁶ is cyano; carbamyl; nitro; acetyl; or carbonalkoxy; and R⁷ is C₁ -C₁₀ -alkyl; C₁ -C₁₀ -alkoxy; phenoxy; benzyloxy; phenyl; chlorine; bromine; nitro; C₁ -C₄ -alkoxycarbonyl; C₁ -C₄ -mono- or dialkylamino; C₁ -C₄ -alkoxyethoxy; C₁ -C₄ -alkyl- or phenylmercapto; C₁ -C₅ -alkanoylamino; monosubstituted or polysubstituted phenyl; C₁ -C₄ -alkyl; C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl; or benzyl.
 2. The compound of claim 1, having the formula: ##STR543## wherein: X¹ is hydroxyl; C₁ -C₄ -alkoxy; C₁ -C₄ -alkylthio, methylsulfonyl, phenylsulfonyl, phenoxy or phenylthio,Z¹ is cyano; a carboxylic ester group; or a substituted carbamyl; Y¹ is cyano; T¹ is formyl, nitro or cyano.
 3. The compound of claim 1, having the formula: ##STR544## wherein: X¹ is hydroxyl; C₁ -C₄ -alkoxy; C₁ -C₄ -alkylthio, methylsulfonyl, phenylsulfonyl, phenoxy or phenylthio,Y¹ is cyano; T¹ is formyl, nitro or cyano; B³ is hydrogen or B⁴ ; and B⁴ is C₂ -C₆ -alkyl; C₂ -C₆ -alkyl interrupted by oxygen; C₂ -C₆ -alkyl interrupted by oxygen and substituted by hydroxyl; C₁ -C₄ -alkanoyloxy; C₁ -C₄ -alkoxy; benzyloxy or phenoxy; or B⁴ is phenyl; or phenyl substituted by methyl or methoxy.
 4. The compound of claim 1, having the formula: ##STR545## wherein: B⁵ is hydrogen; chlorine, methyl; methoxy; or ethoxy;B⁶ is hydrogen; methyl; methoxy; C₁ -C₄ -alkanoylamino; C₁ -C₄ -alkanoylamino substituted by methoxy, ethoxy, phenoxy, chlorine or cyano; B⁷ is hydrogen or B⁸ ; B⁸ is cyclohexyl; benzyl; phenyl; C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted by hydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoyloxy or cyano; X¹ is hydroxyl; C₁ -C₄ -alkoxy; C₁ -C₄ -alkylthio, methylsulfonyl, phenylsulfonyl, phenoxy or phenylthio, Y¹ is cyano; and T¹ is formyl, nitro or cyano.
 5. The compound of claim 1, wherein X is methoxy, ethoxy, phenylthio, methylsulfonyl or phenylsulfonyl and T is formyl.
 6. The compound of claim 1, wherein X is methoxy, ethoxy, phenylthio, methylsulfonyl or phenylsulfonyl and T is cyano.
 7. The compound of claim 1, wherein X is methoxy, ethoxy, phenylthio, methylsulfonyl or phenylsulfonyl and T is nitro.
 8. The compound of claim 1, wherein:X is methoxy, ethoxy, phenylthio, methylsulfonyl or phenylsulfonyl; T is a radical of the formula CH═B, wherein B is ##STR546## and Z is hydrogen, cyano, carboxyl, a carboxylic ester group, carbamyl; benzimidazolyl; benzoxazolyl; benzthiazolyl; substituted carbamyl, substituted benzimidazolyl, substituted benzoxazolyl; or substituted benzthiazolyl.
 9. The compound of claim 1, wherein B² is CH₃, C₂ H₅, C₃ H₇ CH(CH₃)₂, C₄ H₉, CH₂ CH(CH₃)₂, CH(CH₃)--C₂ H₅, C₅ H₁₁, CH(CH₃)--CH(CH₃)₂, CH(C₂ H₅)₂, CH(CH₃)--C₃ H₇, CH(CH₃)--CH(CH₃)₂, C₂ H₄ --CH(CH₃)₂, CH₂ --C(CH₃)₃, C₆ H₁₃, C₂ H₄ OH, C₃ H₆ OH, CH₂ --CH(CH₃)--OH, CH(CH₃)--CH₂ --OH, C₄ H₈ OH, CH(CH₃)--C₂ H₄ --OH, CH(CH₃) --CH₂ --OH, C₆ H₁₂ OH, C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OC₃ H₇, C₂ H₄ OC₄ H₉, C₂ H₄ OC.sub. 6 H₅, C₂ H₄ OC₆ H₁₁, C₂ H₄ CN, C₅ H₁₀ CN, C₆ H₁₂ CN, C₃ H₆ OCH₃, C₃ H₆ OC₃ H₇, C₃ H₆ OCH₂ --CH(C₂ H₅)--C₄ H₉, C₃ H₆ OC₆ H₁₁, C₃ H₆ OC₈ H₁₇, C₃ H₆ OCH₂ C₆ H₅, C₃ H₆ OC₂ H₄ C₆ H₅, C₃ H₆ OC₂ H₄ OC₆ H₅, C₃ H₆ OC₆ H₅, C₃ H₆ OC₂ H₄ OH, C₃ H₆ OC₄ H₆ OH, C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OCH(CH₃)₂, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₂ H.sub. 4 OCH₂ C₆ H₅, C₃ H₆ OC₂ H₄ OC₆ H₅, C₃ H₆ OC₄ H₈ OCH₃, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, CH(CH₃)--CH₂ OCH₃, CH(CH₃)CH₂ OC₄ H₉, CH(CH₃)--CH₂ OC₆ H₅, CH(CH₃) CH₂ OCH₂ C₆ H₅, CH(CH₃)--C₂ H₄ OCH₃, CH(C₂ H₅)--CH₂ --OCH₃, CH(CH₃)--CH(OCH₃)₂, CH₂ CH(CH₃)OCH₃, CH₂ --CH(CH₃)--OC₂ H₅, CH₂ --CH(CH₃)--OC₄ H₉, or CH₂ --CH(CH)--OC₆ H₅.
 10. The compound of claim 1, wherein R³ is methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-b-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl or 2-benzoylethyl.
 11. The compound of claim 1, where R⁶ is aminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- or secbutoxycarbonyl.
 12. The compound of claim 3, wherein B⁴ is C₂ H₅, C₃ H₇, C₄ H₉, CH₂ CH(C₂ H₅)(C₄ H₉), C₆ H₅, C₆ H₄ CH₃, C₃ H₄ OCH₃, C₃ H₆ OCH₃, C₂ H₄ OC₂ H₅, C₃ H₄ OC₄ H₉, C₃ H₆ OC₂ H₅, C₂ H₄ OC₂ H₄ OH, C₃ H₆ OC₂ H₄ OH, C₃ H₆ OC₄ H₈ OH, C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ C₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₂ H₄ OC₂ H₄ OCO(CH₂)_(m) CH₃, C₃ H₆ OC₂ H₄ OCO(CH₂)_(m) CH₃, C₃ H₆ OC₄ H₈ OCO(CH₂)_(m) CH₃, or C₃ H₆ OC₂ H₄ OC₆ H₅, where m is from 1 to
 4. 13. The compound of claim 13, wherein one of B³ and B⁴ is independently C₂ H₄ OC₂ H₄ OCOCH₃, C₂ H₄ OC₂ H₄ OCO[H]C₂ H₅, C₃ H₆ OC₄ H₈ OCOCH₃, C₃ H₆ OC₄ H₈ OCOC₂ H₅, C₃ H₆ OC₂ H₄ OCH₃, C₃ H₆ OC₂ H₄ OC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₃ H₆ OCH₂ C₆ H₅, C₃ H₆ OC₂ H₄ OC₆ H₅, or C₃ H₆ OCH₂ -CH(C₂ H₅)C₄ H₉, C₂ H₅, C₂ H₄ OCH₃, C₃ H₆ OCH₃, CH(CH₃)₂, or C₄ H₉, andthe other of B³ and B⁴ is C₂ H₄ OC₂ H₄ OCOCH₃, C₃ H₆ OC₄ H₈ OCHO, C₃ H₆ OC₄ H₈ OCOCH₃, C₃ H₆ OC₄ H₈ OCOC₂ H₅, C₃ H₆ OC₂ H₄ OC₄ H₉, C₃ H₆ OC₄ H₈ OC₂ H₅, C₃ H₆ OC₄ H₈ OC₄ H₉, C₃ H₆ OC₂ H₄ OC₆ H₅.
 14. A compound of the formula: ##STR547## wherein: X is SO₂ E; --OH; --SH; C₁₋₆ -alkoxy; benzyloxy; phenyloxy; methyl-substituted phenyloxy; chloro-substituted phenyloxy; --S--(C₁₋₆ -alkyl); benzylmercapto; --S--C₂ H₄ OH; --S--CH₂ COOCH₃ ; --S--CH₂ COOC₂ H₅ ; phenylmercapto; or methyl-substituted phenylmercapto;E is C₁₋₈ -alkyl; C₇₋₁₀ -aralkyl; phenyl; chloro-substituted phenyl; chlorine; hydroxyl; amino; C₁₋₄ -alkoxy; benzyloxy; C₆ H₅ --CH₂ CH₂ --O--; phenyloxy; chlorosubstituted phenyloxy; methyl-substituted phenyloxy; mono-C₁₋₄ alkyl-substituted amino; di-C₁₋₄ alkyl-substituted amino; NHC₆ H₅ ; NHC₆ H₄ CH₃ ; NHC₆ H₄ Cl; or N(CH₃)C₆ H₄ ; Y is cyano; T is hydrogen; C₁ -C₄ -alkyl; Cl; Br; NO; NO₂ ; SO₃ H; CHO; CN; CH₃ CO; C₂ H₅ CO; C₆ H₅ CO; CH₃ SO₂ ; C₂ H₅ SO₂ ; or C₆ H₅ SO₂ ; or --CH═B; R¹ is hydrogen, alkyl, aralkyl or aryl; B is C(CN)(Z) where Z is cyano; nitro; C(O)CH₃ ; benzoyl; methylsulfonyl; phenylsulfonyl; carboxyl; a C₁₋₄ -alkyl or phenyl carboxylic ester group; unsubstituted carbamyl; C₁₋₂ -alkyl or phenyl substituted carbamyl; or a compound of one of the formulae: ##STR548## and K is a radical derived from a coupling component of the formula: ##STR549## wherein: B¹ is hydrogen or B² ; B² is C₁ -C₆ -alkyl, or C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy, or phenylethoxycarbonyl, or phenyl, or cyclohexyl; R² is hydrogen or R³ ; R³ is C₁ -C₆ -alkyl, C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, phenoxy, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m-and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenylethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy, or phenylethoxycarbonyl, phenyl, benzyl, phenethyl, or cyclohexyl; R⁴ and R⁵, independently of one another, are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, or C₁ -C₄ -alkoxycarbonylamino, benzoylamino, C₁ -C₆ -alkanoylamino, or C₁ -C₆ -alkanoylamino substituted by chlorine, bromine, cyano, methoxy, ethoxy, or phenoxy, C₁ -C₄ -alkylsulfonylamino, or -dialkylaminosulfonylamino; R⁶ is cyano; carbamyl; nitro, acetyl; or carbonalkoxy; and R⁷ is C₁ -C₁₀ -alkyl; C₁ -C₁₀ -alkoxy; phenoxy; benzyloxy; phenyl; chlorine; bromine; nitro; C₁ -C₄ -alkoxycarbonyl; C₁ -C₄ -mono- or dialkylamino; C₁ -C₄ -alkoxyethoxy; C₁ -C₄ -alkyl- or phenylmercapto; C₁ -C₅ -alkanoylamino; monosubstituted or polysubstituted phenyl; C₁ -C₄ -alkyl; C₁ -C₄ -alkoxycarbonylmethyl, cyanomethyl; or benzyl. 